Rotational spectra of ortho‐nitrotoluene (2‐NT) and para‐nitrotoluene (4‐NT) have been recorded at low and room temperatures using a supersonic jet Fourier Transform microwave (MW) spectrometer and a millimeter‐wave frequency multiplier chain, respectively. Supported by quantum chemistry calculations, the spectral analysis of pure rotation lines in the vibrational ground state has allowed to characterise the rotational energy, the hyperfine structure due to the 14 N nucleus and the internal rotation splittings arising from the methyl group. For 2‐NT, an anisotropic internal rotation of coupled −CH 3 and −NO 2 torsional motions was identified by quantum chemistry calculations and discussed from the results of the MW analysis. The study of the internal rotation splittings in the spectra of three NT isomers allowed to characterise the internal rotation potentials of the methyl group and to compare them with other mono‐substituted toluene derivatives in order to study the isomeric influence on the internal rotation barrier.